Process for forming a patterned thin film structure for in-mold decoration

ABSTRACT

A process for forming a patterned thin film structure on a substrate or in-mold decoration film is disclosed. A pattern is printed with a material, such as a masking coating or ink, on the substrate, the pattern being such that, in one embodiment, the desired structures will be formed in the areas where the printed material is not present, i.e., a negative image of thin film structure to be formed is printed. In another embodiment, the pattern is printed with a material that is difficult to strip from the substrate, and the desired thin film structures will be formed in the areas where the printed material is present, i.e., a positive image of the thin film structure is printed. The thin film material is deposited on the patterned substrate, and the undesired area is stripped, leaving behind the patterned thin film structure.

This application is a continuation-in-part of U.S. application Ser. No.10/665,992, filed Sep. 19, 2003; which is a continuation-in-part of U.S.application Ser. No. 10/422,557, filed Apr. 23, 2003, which claims thebenefit of U.S. Provisional Application No. 60/375,902, filed Apr. 24,2002; the contents of the above applications are incorporated herein byreference in their entirety.

FIELD OF THE INVENTION

The present invention relates generally to in-mold decoration. A processfor forming a patterned thin film on a substrate for in-mold decorationis disclosed.

BACKGROUND OF THE INVENTION

In-mold decoration (IMD) has emerged as an increasingly popular set oftechniques for decorating injection-molded parts. IMD techniques areused to incorporate text, numbers, legends, other symbols andinformation, and purely decoratively designs into injection molded partssuch as telephones and other consumer electronics, automobiledashboards, containers and packaging for consumer products, and indeedthe full spectrum of injection molded parts.

IMD typically involves creating an in-mold decoration film (IMD film orIMD decorated film) comprising the image to be transferred to orintegrated with a surface of the injection-molded part. In a typicalin-mold transfer process, a polyethylene terephthalate (PET) film istreated with a release agent (to facilitate image transfer) and thencoated with a durable layer to provide oil and scratch resistance. Thedecoration is then printed and/or otherwise formed on the treated andcoated PET film, followed by coating the film with an adhesive (e.g.,hot melt or polyurethane adhesive) to form the in-mold transfer film.The film is then inserted into the injection mold prior to injection ofthe molten resin, and the decoration (or other image) is transferredfrom the PET film to the injection-molded item. In a typical in-moldinsert process, the decoration or other image is not transferred fromthe IMD decorated film to the injection-molded item but instead the IMDdecorated film is bonded to and becomes a part of the injection-moldeditem. In one typical in-mold insert process, a polycarbonate (PC)substrate is used. The decoration or other image to be included on theinjection-molded item is printed or otherwise formed on a surface of thePC substrate. The patterned substrate is then coated with a thinprotective layer (to protect the ink from damage during the injectionprocess) to provide the IMD decorated film.

In some cases, IMD techniques may be used to apply or incorporate intoan injection-molded item a decoration or other image that comprises apatterned metal thin film or other thin film material. In one approach,such a patterned thin film design is incorporated by forming a patternedmetal thin film layer on the IMD decorated film. One typical prior artapproach to fabricating an in-mold decoration film comprising apatterned metal thin film involves the use of photolithographictechniques and chemical etching. The typical photolithographic processcomprises several time consuming and high cost steps including (1)forming an unpatterned metal thin film layer (2) coating the metal thinfilm with photoresist; (3) patterning the photoresist by image-wiseexposing it through a photomask to, for example, ultraviolet light; (4)“developing” the patterned image by removing the photoresist from eitherthe exposed or the unexposed areas, depending on the type of photoresistused, to uncover the metal thin film in areas from which it is to beremoved (i.e., areas where no thin film material is to be located); (5)using a chemical etching process to remove the thin film from the areasfrom which the photoresist has been removed; and (6) stripping theremaining photoresist to uncover the patterned thin film structures.

Certain of the processing steps under the photolithographic approach,such as the image-wise exposure, are time consuming and require carefulregistration and alignment of the mask and the moving target area. Inaddition, development and stripping of photoresist and treatment ofwaste from the chemical etching process may be time consuming andexpensive, in addition to potentially posing an environmental hazard.The chemical etching process also tends to result in a less shiny metalsurface, which is often undesirable for high-end decorationapplications.

Therefore, there is a need for a process for forming patterned thin filmstructures on a plastic substrate for use as an IMD decorated film thatdoes not require the use of photolithography or chemical etching.

BRIEF DESCRIPTION OF THE DRAWINGS

The present invention will be readily understood by the followingdetailed description in conjunction with the accompanying drawings,wherein like reference numerals designate like structural elements, andin which:

FIG. 1 is a flowchart illustrating a process used in one embodiment toform a patterned thin film on a substrate.

FIGS. 2A through 2D illustrate a schematic plan view of a series ofprocessing steps used to form four metal stripes on a substrate.

FIGS. 3A through 3D further illustrate the example shown in FIGS. 2Athrough 2D by providing a schematic front cross-sectional view of theprocessing steps shown in FIGS. 2A through 2D.

FIGS. 4A and 4B illustrate a schematic plan view of an example in whichsegment electrodes for a seven segment pattern are formed using anembodiment of the process described herein.

FIGS. 5A-1 through 5D-2 illustrate an alternative process used in oneembodiment to form a patterned thin film on a substrate.

FIGS. 6A-1 through 6F-2 illustrate a further alternative to the processshown in FIGS. 1-4.

FIG. 7 illustrates typical process steps for the making of an in-mold(transfer) decoration film.

FIG. 8 illustrates typical steps for the making of an in-mold labelingor insertion film.

DETAILED DESCRIPTION

A detailed description of a preferred embodiment of the invention isprovided below. While the invention is described in conjunction withthat preferred embodiment, it should be understood that the invention isnot limited to any one embodiment. On the contrary, the scope of theinvention is limited only by the appended claims and the inventionencompasses numerous alternatives, modifications and equivalents. Forthe purpose of example, numerous specific details are set forth in thefollowing description in order to provide a thorough understanding ofthe present invention. The present invention may be practiced accordingto the claims without some or all of these specific details. For thepurpose of clarity, technical material that is known in the technicalfields related to the invention has not been described in detail so thatthe present invention is not unnecessarily obscured.

A process for forming a patterned thin film structure on a substrate isdisclosed. In one embodiment, the thin film material may be conductive,non-conductive, or semi-conductive. In one embodiment, the patternedthin film structure comprises a metallic or metal-based design formed ona polymer substrate for use as an IMD decorated film. A pattern isprinted with a masking coating or an ink, on the substrate, the patternbeing such that, in one embodiment, the desired thin film structureswill be formed in the areas where the printed masking coating is notpresent, i.e., a negative image of thin film structure to be formed isprinted. The masking layer comprises 5-80% by weight, preferably 10-60%by weight based on dried weight of the masking layer, of re-dispersibleparticulates uniformly dispersed in a binder that is soluble ordispersible in the stripper composition used in the subsequent strippingprocess. A re-dispersible particulate is defined as a particulate thatis dispersible in the stripping solution used to remove the maskingcoating/ink. A particulate that is not re-dispersible tends to result inundesirable scum or dirty background after stripping. A thin film isdeposited uniformly by, for example, vapor deposition or sputtering,onto the substrate preprinted with the masking ink. The thin film on themasking coating as well as the masking coating are then removed in thesubsequent stripping step.

In another embodiment, a masking layer is first uniformly coated on thesubstrate and a tie or anchoring material that is difficult to stripfrom the substrate, is printed in a pattern onto the masking layer. Thetie coat has a good adhesion to both the masking layer and the thin filmto be deposited on the patterned substrate. The thin film material notdeposited on the tie coat is then selectively stripped, leaving behindthe patterned thin film design. In this case, the desired thin filmstructure is formed in the areas where the printed tie material ispresent, i.e., a positive image of the thin film structure is printed.

FIG. 1 is a flowchart illustrating a process used in one embodiment toform a patterned thin film structure on a substrate. The process beginsin step 102 and proceeds to step 104 in which a negative image of thethin film structures to be formed is printed on the surface of thesubstrate using a masking coating or ink. In one embodiment, the maskingcoating or ink may be stripped using an aqueous solution and/or anothercommon solvent. In step 104, a negative image of the thin filmstructures to be formed is printed in the sense that the masking coatingor ink will cover areas of the substrate where the thin film materialwill not be present upon completion of the process and will not coverareas of the substrate where the thin film material will be present. Inessence, the ink pattern serves as a mask for the subsequent depositionof thin film material, as described more fully below in connection withstep 106.

Any suitable printing techniques, such as flexographic, driographic,electro photographic, and lithographic printing, may be used to printthe ink pattern on the substrate. In certain applications, otherprinting techniques, such as stamping, screen printing, gravureprinting, ink jet, and thermal printing may be suitable, depending onthe resolution required. In addition, the masking coating or ink doesnot need to be optically contrasted with the substrate, and can becolorless.

In one embodiment, the masking coating or ink comprises a re-dispersibleparticulate. In one embodiment, the masking coating or ink comprises5-80% by weight, preferably 10-60% by weight based on dried weight ofthe masking layer, of a re-dispersible particulate and a binder solubleor dispersible in the stripper composition. In one embodiment, themasking coating or ink comprises a water-soluble or water-dispersiblepolymer as a binder. Typical examples of water soluble polymers include,but are not limited to, polyvinyl alcohol, polyvinylpyrrolidone,polyvinyl pyridine, polyacrylic acid, polymethacrylic acid,polyacrylamide, polyethylene glycol, poly(ethylene-co-maleic anhydride),poly (vinyl ether-co-maleic anhydride), poly(styrene-co-maleicanhydride), poly(butyelene-co-itaconic acid), PEOX, polystyrenesulfonate, cellulose derivatives such as hydroxyethyl cellulose,hydroxypropyl cellulose, methyl cellulose, carboxymethyl cellulose,xanthan gum, gum Arabic, gelatin, lecitin, and their copolymers. In onesuch embodiment, the water-dispersible polymer comprises a water- oralkaline-dispersible wax, polyolefin, or acrylic latexes or dispersions.In one embodiment, the masking coating or ink comprises asolvent-soluble or solvent-dispersible polymer as a binder. In oneembodiment, the masking coating or ink comprises a re-dispersibleparticulate derived from silica, CaCO₃, CaSO₄, BaSO₄, Al₂O₃, TiO₂,hollow-spheres, non-film-forming latexes or dispersions, inorganicpigment(s), or organic pigment(s). In one embodiment, the maskingcoating or ink comprises a re-dispersible particulate comprising apolymeric or polymeric composite particle. In one embodiment, includinga re-dispersible particulate in the masking coating or ink facilitatessubsequent stripping of the masking coating or ink. In one embodiment,including a re-dispersible particulate in the masking coating or inkfacilitates subsequent stripping of the masking coating or ink byreducing the thickness or integrity of the masking coating or ink layerand/or improving the permeation of a stripping solvent into the maskingcoating or ink layer during stripping.

In step 106, a thin film of material is deposited on the patternedsurface of the substrate. In one embodiment, the thin film material maybe conductive, non-conductive, or semi-conductive. In one embodiment,vapor deposition is used to deposit the thin film of material on thepatterned side of the substrate in step 106. In such an embodiment,aluminum, copper, or any material suitable for being deposited as a thinfilm through vapor deposition or spraying may be used as the thin filmmaterial. In one alternative embodiment, the thin film material isdeposited by sputter coating the patterned side of the substrate withthe thin film material. In such an embodiment, indium tin oxide (ITO),zinc sulfide, gold, silver, copper, iron, nickel, zinc, indium,chromium, aluminum-doped zinc oxide, gadolinium indium oxide, tin oxide,or fluorine-doped indium oxide, or any other material suitable for beingdeposited in a thin film through sputter coating may be used.

Any process for forming a thin film layer on the patterned substrate maybe used, including without limitation by laminating, electroplating,sputtering, vacuum deposition, or combinations of more than one processfor forming a thin film onto a plastic substrate. Useful thin filmconductors include metal conductors such as, for example, aluminum,copper, zinc, tin, molybdenum, nickel, chromium, silver, gold, iron,indium, thallium, titanium, tantalum, tungsten, rhodium, palladium,platinum and/or cobalt, etc., and metal oxide conductors such as indiumtin oxide (ITO) and indium zinc oxide (IZO), as well as alloys ormultilayer composite films derived from the aforementioned metals and/ormetal oxides. Further, the thin film structures described herein maycomprise either a single layer thin film or a multi-layer thin film.Useful plastic substrates include epoxy resins, polyimide, polysulfone,polyarylether, polycarbonate (PC), polyethylene terephthalate (PET),polyethylene terenaphthalate (PEN), poly(cyclic olefin), and theircomposites. For in-mold decoration, the substrate is typically coatedwith a release layer (not shown), which is subsequently overcoated witha durable layer (not shown). A pattern of masking coating is printedonto the durable layer. The printed multilayer film is then overcoatedby, for example, vapor deposition or sputtering, with a thin film.

In step 108 of the process shown in FIG. 1, the masking coating or inkis stripped from the patterned surface of the substrate on which thethin film material has been deposited in step 106. The stripping of thecoating/ink in step 108 has the effect of stripping away the printedpattern formed in step 104 as well as the portion of the thin filmmaterial deposited in step 106 that was deposited on to the areas of thesubstrate where the coating/ink was present. As a result, the strippingsolvent is able to strip away the coating/ink pattern and the thin filmmaterial formed on the top surface of the coating/ink pattern, eventhough the stripping step is performed after the deposition of the thinfilm in step 106. The process shown in FIG. 1 then ends in step 110.Without limiting the generality of the present disclosure, it isbelieved that in certain embodiments at least part of the maskingcoating/ink printed in step 104 is exposed, or nearly so, to thestripping solvent, despite the masking patterns having been covered withmetal thin film as a result of the deposition process of step 106. Inone embodiment, the masking coating or ink comprises 5-80% by weight,preferably 10-60% by weight based on dried weight of the masking layer,of a re-dispersible particulate and a binder soluble or dispersible inthe stripper composition.

The masking coating preferably meets certain conditions in order to becommercially useful. Because the masking coating is used in amanufacturing process which is usually carried out roll-to-roll, themasking coating needs to be rolled up in the process. To accommodatethis manufacturing condition, the masking coating has to be non-blocking(i.e., layers do not stick together). Secondly, the stripping speed ofthe masking coating is critical to the production yield. However, thesetwo conditions are difficult to meet at the same time.

Because most of the commonly used stripping solutions are water-based,the masking coating is usually formed of a water soluble polymermaterial. Polymeric materials of a high molecular weight, however, areoften slow in dissolution. In order to speed up stripping, certainsolubility enhancers of a low molecular weight have to be added.Alternatively, lower molecular weight polymers with a higher solubilitymay be used. These low molecular weight materials, however, often causethe film blocking phenomenon. While the blocking problem may bealleviated by incorporating particulate materials, the presence ofinorganic particles, however, usually reduces film solubility, thusreducing the stripping speed.

It has now been found that when certain types of re-dispersibleparticulate materials are incorporated into a masking coating, bothconditions described may be satisfied at the same time, without using asolubility enhancer. The term “re-dispersible particulate” is derivedfrom the observation that the presence of these particles in asignificant quantity will not decrease the stripping ability of a driedmasking coating and, on the contrary, their presence actually enhancesthe stripping speed of the dried masking coating.

The re-dispersible particulate is particles that are surface treated tobe hydrophilic through anionic, cationic, or non-ionic functionalities.Their sizes are in microns, preferably in the range of about 0.1 to toabout 15 um and more preferably in the range of about 0.3 to about 8 um.Particles in these size ranges have been found to create proper surfaceroughness on a masking coating having a thickness of <15um. There-dispersible particulate may have a surface area in the range of about50 to about 500 m²/g, preferably in the range of about 200 to about 400m²/g. The interior of the re-dispersible particulate may also bemodified to have a pore volume in the range of about 0.3 to about 3.0ml/g, preferably in the range of about 0.7 to about 2.0 ml/g.

Suitable re-dispersible particulate for the present invention mayinclude, but are not limited to, micronized silica particles, such asthose of the Sylojet series or Syloid series from Grace Davison,Columbia, Md., USA.

Non-porous nano sized water re-dispersible colloid silica particles,such as LUDOX AM can also be used together with the micron sizedparticles to enhance both the surface hardness and stripping rate of themasking layer.

Other organic and inorganic particles, with sufficient hydrophilicitythrough surface treatment, may also be suitable. The surfacemodification can be achieved by inorganic and organic surfacemodification. The surface treatment provides the dispersibility of theparticles in water and the re-wet ability in the masking coating.

The presence of the re-dispersible particulates as describeddramatically improves the stripability of the thin film on the maskingcoating as well as the blocking resistance of the masking coated films,particularly at high temperature and humidity conditions.

In one embodiment, low molecular weight additives such as plasticizers,surfactants, and residual monomers or solvents in the maskingcoating/ink may cause defects or micro-porosity in the metal coated onthe ink, accelerating exposure of the masking coating to the solvent.The present disclosure contemplates that any suitable combination ofcoating/ink, thin film, and stripping process may be used, withoutlimiting the applicability of the present disclosure in any way, andwithout limiting the present disclosure to any particular strippingmechanism or theory. With respect to the process shown in FIG. 1, theonly requirement is that the combination used be such that uponstripping the areas of thin film formed on the substrate remain presentand the areas of thin film formed on the strippable masking coating/inkbe stripped away, or largely so, such that after stripping the thin filmstructures are not present in areas where the coating/ink pattern waspresent, or sufficiently nearly so for the desired design to beportrayed adequately.

The process described above does not require the use of photolithographyand selective etching of the conductive layer to define patterned thinfilm structures on a substrate. Instead, the ink pattern is used todefine, prior to the deposition of the thin film material, the shape ofthe thin film structures to be formed. Depending on the durable layerused in the in-mold decoration film, a simple solvent, such as water,aqueous solutions, alcohols, ketones, esters, DMSO, or many other commonorganic solvents or solvent mixture, may be used to strip away the inkand the thin film material formed on top of the ink pattern. An aqueousstripper is preferred because of the environmental issues. The patternedthin film structures may be formed via a roll-to-roll process that isnot as time consuming, not as expensive, and does not generate as muchtoxic chemical waste as the photolithographic and chemical etchingtechniques used in prior art photolithographic processes.

As noted above, the techniques described herein may be used in oneembodiment to create an IMD decorated film comprising a patternedmetallization or other patterned thin film layer. FIGS. 2A through 2Dillustrate a schematic plan view of a series of processing steps used toform on a substrate using thin film structures a simple designcomprising four vertical lines. FIG. 2A shows a plastic substrate 202.In FIG. 2B an ink pattern comprising lines 204 has been printed on thesubstrate 202. In the example shown in FIG. 2B the lines 204 define onthe substrate 202 areas on which four vertical thin film structures willbe formed, as described more fully below, in the areas of substrate 202that are not covered by the lines 204.

In FIG. 2C, a thin film layer 206 has been formed on the patternedsurface of the substrate, covering both the portions of the substrate202 that are not covered by the ink lines 204 (shown by dashed lines inFIG. 2C) and the portions that are covered by the ink lines 204. In FIG.2D, the ink pattern has been stripped away, along with the portions ofthe thin film 206 that were deposited on the ink lines 204, exposingthin film structures 208. The respective thin film structures 208 areseparated from each other by the areas of the substrate 202 exposed bythe stripping away of the ink lines 204.

FIGS. 3A through 3D further illustrate the example shown in FIGS. 2Athrough 2D by providing a schematic front cross-sectional view of theprocessing steps shown in FIGS. 2A through 2D. FIG. 3A shows a frontcross-sectional view of the substrate 202. FIG. 3B shows the ink lines204 formed on the substrate 202. As shown in FIG. 3C, the thin filmlayer 206 forms on the portions of the substrate not covered by thelines 204 and on the top and side surfaces of the polymer ink lines 204.Finally, FIG. 3D shows the thin film structures 208 that remain formedon the substrate 202 subsequent to the stripping of the lines 204, whichhas the effect of stripping away both the ink lines 204 and any thinfilm material 206 formed on top of the ink lines 204.

While FIGS. 2A-2D and 3A-3D illustrate an example in which four verticalthin film structures are formed on a plastic substrate, the coating/inkmay be printed in any arbitrary pattern to define on the substrate thinfilm structures of any desired shape or size. FIGS. 4A and 4B illustratea schematic plan view of an example in which segments forming the number“8” are formed using an embodiment of the process described herein. FIG.4A shows the IMD decorated film 400 comprising a masking ink pattern 402defining on a plastic substrate seven thin film segment areas 404 a-404g in which the ink pattern 402 is not present such that the underlyingsubstrate is exposed. FIG. 4B shows the same film 400 subsequent to thesteps of deposition of the thin film and stripping of the ink pattern.As shown in FIG. 4B, the stripping away of the ink exposes a backgroundarea 406 of the substrate on which no thin film structure is present. Inaddition, thin film segments 408 a-408 g have been formed and remain inthe segment areas 404 a-404 g defined as described above in connectionwith FIG. 4A.

As is apparent from the above discussion, thin film structures of anyshape or size may be formed simply by defining through use of theprinted pattern areas on the substrate on which thin film structures areto be formed.

In one embodiment of the process illustrated in FIGS. 1-4, thecoating/ink used to pattern the substrate comprises Sun ChemicalAquabond AP blue ink and/or Sunester red ink (Sun Chemical, Northlake,Ill.) and the substrate comprises 5 mil thick Melinex 453 polyester(DuPont Teijin, Hopewell, Va.). The ink may be applied through a stencilusing a hand proofer with a #360 anilox roller. The ink may be driedwith a heat gun. The metal thin film is deposited by loading thepatterned substrate into a DC-magnetron sputtering system to deposit ITOfilm up to about 100 nm thickness. The patterned substrate may be plasmatreated prior to deposition of the metal thin film. The ink pattern andmetal thin film formed thereon is stripped by spraying the patternedsubstrate on which the metal thin film has been formed with acetone(Histological grade, Fisher Scientific) for 1 to 2 minutes at roomtemperature. The above processing steps result in the metal thin film(i.e., ITO) formed in the ink pattern being removed along with the ink,leaving an area on the substrate where no ITO coating is present suchthat no measurable conductivity in present in such areas where the ITOhas been removed.

In one embodiment of the processes illustrated in FIGS. 1-4, Film IIIWarm Red ink (Environmental Inks and Coatings, Los Angeles, Calif.) isapplied using a hand proofer to define a pattern or mask on a substratecomprising 5 mil thick Melinex ST505 polyester (DuPont Teijin, Hopewell,Va.). The metal thin film is deposited by loading the patternedsubstrate into a DC-magnetron sputtering system to deposit ITO film upto about 100 nm thickness. The ink is washed from the ITO coatedpatterned substrate by spraying with acetone (Histological grade, FisherScientific) for 30 to 60 sec. The ITO formed on the ink is removed alongwith the ink, leaving an area where there is no ITO coating where theink pattern was printed.

In one embodiment of the processes illustrated in FIGS. 1-4, the maskingink pattern is printed on 5 mil thick, 4507 Polyester (Transilwrap,Franklin Park, Ill.) using GP-217 Process Magenta ink (Ink Systems Inc.,Commerce, Calif.) on an offset press. The inked polyester is loaded in avacuum system for aluminum evaporation at the film thickness of 120 nm.The aluminum-coated polyester is immersed in hot (T=about 80° C.) methylethyl ketone (Certified grade, Fisher Scientific, MEK) for 15 seconds,and then wiped gently with a cotton swab soaked in MEK. This processstrips the inked area from the polyester, along with the aluminum on topof the ink. The stripping results in a negative image from the ink,i.e., there is no aluminum coating in the areas where the ink patternwas printed, with the remaining areas (i.e., where the ink pattern wasnot present) being coated with aluminum.

In one embodiment of the processes illustrated in FIGS. 1-4, a maskingink pattern is made on a roll of 5 mil thick, 12″ wide Melinex 453polyester (Plastics Suppliers, Fullerton Calif.) using Film III Warm Redink (Environmental Inks and Coatings, Los Angeles, Calif.) on a MarkAndy 4200 flexographic press. The patterned polyester is loaded into aDC-magnetron sputtering system to deposit ITO film for about 100 nm.Prior to the deposition, the ink-coated sheets may be plasma treated.The ITO coated polyester is then immersed in a jar of hot (T=about 80°C.) MEK and cleaned ultrasonically using a Fisher Scientific FS220Hultrasonic cleaner for 2 minutes. As a result of the ultrasonic cleaningstep, the ink is stripped from the polyester, along with the ITO formedon top of the ink.

The ability to strip away the masking coating/ink lines after depositionof the metal thin film using a simple stripping process that is notdestructive of the thin film formed in the areas where the coating/inkpattern is not present (such as but not limited to the solvent andphysical peeling processes described above) facilitates a continuousfabrication process, such as a roll to roll fabrication process, becauseno time consuming batch processes such as image-wise exposure anddevelopment of photoresist, etching away portions of a thin film layernot covered by photoresist, or using solvents requiring special handlingor conditions to remove a photoresist layer after etching, are required.By saving time and using less expensive materials, the process describedherein is much less costly than other processes typically used to formon a polymer substrate the types of structures described herein. Thepresence of a redispersible particulate in the masking coating/inksignificantly improves the blocking resistance of the coated film and inturn widens the process window of the roll-to-roll process. Moreover,the redispersible particulate greatly improves the strip-ability of thethin film deposited on the masking coating/ink.

FIGS. 5A-1 through 5D-2 illustrate an alternative process used in oneembodiment to form a patterned thin film design on a substrate. Thealternative process shown in FIGS. 5A-1 through 5D-2 employs a“positive” printed image in the sense that the coating/ink is printed inthe pattern of the thin film structure(s) to be formed, instead of beingused as described above in connection with FIGS. 1-4 to define areaswhere the thin film structure(s) is/are not to be formed. The processillustrated in FIGS. 5A-1 through 5D-2 is similar to that shown in FIGS.1-4 in that the process shown in FIGS. 5A-1 through 5D-2 employsprinting techniques to define the thin film structure(s) to be formed.The process shown in FIGS. 5A-1 through 5D-2 differs from the processshown in FIGS. 1-4, however, in that the printed pattern is not strippedoff the substrate, as described more fully below.

As shown in FIGS. 5A-1 and 5A-2, the thin film structures are formed ona substrate 502. The substrate 502 may be any of the substrate materialsdescribed above for use in the process illustrated by FIGS. 1-4. In oneembodiment, the substrate comprises 5 mil thick, 4507 Polyester(available from Transilwrap, Franklin Park, Ill.). FIGS. 5B-1 and 5B-2show pattern lines 504 and 506 printed on the substrate 502. In oneembodiment, the pattern lines 504 and 506 are printed on the substrate502 using GP20011 UV Process Magenta ink (Ink Systems Inc., Commerce,Calif.) on an offset press. Any ink or other printable material may beused that has the characteristic that the subsequently deposited thinfilm adheres to the printed material more strongly than it adheres tothe substrate, as explained more fully below.

FIGS. 5C-1 and 5C-2 show a thin film layer 508 being formed on thepatterned surface of the substrate, covering both the printed pattern(lines 504 and 506) and the areas of the substrate 502 not covered bythe printed pattern. In one embodiment, the thin film 508 is formed byloading the patterned substrate into a vacuum system for aluminumevaporation at a film thickness of 120 nm.

FIGS. 5D-1 and 5D-2 show the remaining structures after the portions ofthe thin film 508 formed on the substrate 502 have been removed by astripping process. Thin film structures 510 and 512 remain formed onprinted lines 504 and 506, respectively. In one embodiment, a solvent isused to remove the portions of the thin film formed directly on thesubstrate, but not the portions of the thin film formed over the printedmaterial, leaving thin film structures in the same pattern as theprinted material. In one embodiment, not shown in FIGS. 5D-1 and 5D-2,some or all of the thin film formed on the side surfaces of the printedmaterial remains adhered to the side surfaces of the printed materialafter the stripping process. In one embodiment, not all of the thin filmformed directly on the substrate is removed by the stripping process,but the thin film formed directly on the substrate is removedsufficiently to cause there to be little or no thin film materialvisible in the areas of the substrate where the printed material was notprinted.

The alternative process shown in FIGS. 5A-1 through 5D-2 requires thatthe adhesion of the thin film layer to the substrate be low, theadhesion of the thin film layer to the printed material be high, theadhesion of the printed material to the substrate be high, and that thesolvent be such that it removes the portions of the thin film layer thatare formed directly on the substrate but not those portions of the thinfilm layer formed on the printed material.

In another alternative but preferred process, a semi-finished IMD filmcomprising a substrate, a release layer, and a durable layer with a pooraffinity toward the thin film may be used. In one such embodiment, asurface treatment, tie coating or primer coating such as a UV curablepolymer layer, having good adhesion to both the durable layer and thethin film may be used. In this case, the thin film on the uncoated areaswill be removed in the stripping process to reveal the design on the topof the surface treatment or primer coating. This alternative process issimilar to that shown in FIGS. 5A-1 through 5D-2, with the tie or primercoating (not shown) comprising the printed material, such as patternlines 504 and 506. If the durable layer shows a high affinity toward thethin film, a masking coating/ink may be coated uniformly onto thedurable layer before the tie coat and the printed material. The thinfilm on the area without the printed material will be removed in thestripping process to reveal the design on the top of the printedmaterial and the tie coat.

FIGS. 6A-1 through 6F-2 illustrate a further alternative to the processshown in FIGS. 1-4. FIGS. 6A-1 and 6A-2 show a substrate 602. In FIGS.6B-1 and 6B-2, pattern lines 604 and 606 have been printed onto thesubstrate 602 using a printable first material. In one embodiment, asshown in FIGS. 6C-1 and 6C-2, the printed substrate is then over-coatedwith a second material that is not soluble in at least one solvent inwhich the first printable material is soluble, such that said at leastone solvent could be used to strip the first printable material withoutalso stripping the second material. In one embodiment, the printablefirst material is hydrophobic (i.e., water repelling) and solventsoluble and has a low surface tension. In one embodiment, the secondmaterial is water-based and is repelled by the first material, such thatthe overcoat adheres only to those portions of the substrate not coveredby the first material, forming areas 608, 610, and 612 comprising thesecond (water-based) material. In one alternative embodiment, the secondmaterial is not repelled by the first material and the second materialmay partially or fully overcoat the pattern lines 604 and 606 shown inFIGS. 6C-1 and 6C-2. In one such embodiment, in the regions in which thesecond material overcoats the first material, the second material may beless thick than in regions in which the second material is applieddirectly to the substrate (i.e., regions on the substrate in which thefirst material is not printed). In one embodiment, the first material isstripped using a suitable solvent that does not also strip away thesecond material, leaving the structure shown in FIGS. 6D-1 and 6D-2, inwhich the structures 604 and 606 comprising the first material have beenstripped away, leaving the structures 608, 610, and 612 comprising thesecond material on the substrate 602. In one embodiment in which thesecond material may overcoat, at least in part, the printed firstmaterial, portions of the second material so formed on the firstmaterial are stripped away along with the portions of the first materialon which they are formed, leaving the portions of the second materialapplied directly to the substrate (i.e., in regions where the firstmaterial was not present), as shown in FIG. 6D-1 and 6D-2. In oneembodiment, the solvent used to strip away the first printable material(and, if applicable, portions of the second material formed thereon)comprises an aqueous solution or water. In one embodiment, the solventused to strip away the first printable material comprises a non-aqueoussolvent or solution. Next, as shown in FIGS. 6E-1 and 6E-2, a thin film614 is formed both on the structures 608, 610, and 612 and on theportions of the substrate 602 not covered by the second material, usingone of the thin film materials described above. In one embodiment, thethin film is formed by sputtering, vapor deposition, spraying, or someother suitable technique. Finally, FIGS. 6F-1 and 6F-2 show the thinfilm structures 616 and 618 that remain after the second material hasbeen stripped away with an appropriate solvent, or another appropriatechemical or mechanical stripping process. In one embodiment, the solventused to strip away the first material is an aqueous basic solution andthe solvent used to strip away the second material is an aqueous acidicsolution, an aqueous neutral solution, or water. In one embodiment, thesolvent used to strip away the first material is an aqueous acidicsolution and the solvent used to strip away the second material is anaqueous basic solution, an aqueous neutral solution, or water. In oneembodiment, the solvent used to strip away the first material is anaqueous neutral solution or water and the solvent used to strip away thesecond material is an aqueous acidic solution or an aqueous basicsolution.

Under the process shown in FIGS. 6A-1 through 6F-2, the printed patternof the first material comprises a positive image of the thin filmstructures to be formed. Once the first material has been stripped away,as described above, the remaining second material comprises a negativeimage of the thin film structures to be formed. In a sense, the firstmaterial may be considered a mask that may be used to define areashaving very small dimensions, such as very fine lines, in which the thinfilm structures will not be present. While it may be difficult withpractically useful printing techniques, such as flexographic, to printsuch narrow lines in the first instance, for example because of physicallimitations, spreading of the ink after printing, etc., such techniquesmay be used readily to print less fine lines or less small areas withonly small gaps separating the lines or areas. A second material such asdescribed above may then be used to fill in the narrow spaces betweenthe areas covered by the first material, which first material may thenbe stripped away using an appropriate solvent, leaving behind very finelines or other shapes comprising the second material, which very finelines or shapes it may not have been practical to print in the firstinstance. These lines may then be used, as described above, as anegative image for the formation of adjacent thin film structuresseparated by very narrow gaps, for example.

In one embodiment, a physical stripping process such as peeling is usedto reveal the patterned thin film structures. For example, an adhesivetape having an appropriate cohesion strength and adhesion strength toITO is laminated onto an ITO/PET film pre-printed with a maskingcoating/ink. A subsequent peeling will remove the ITO either on the areaprinted with masking ink or on the area without the ink depending on thecohesion strength of the ink and the adhesion strengths at the ink-PETand ITO-PET interfaces. This stripping technique may be used with any ofthe processes described above.

In one embodiment, the process of FIGS. 6A-1 through 6F-2 comprisesprinting a positive image of desired conductive thin film structures ona roll of Melinex 582 polyester (4 mil thick, 14″ wide, Dupont TeijinFilms, Wilmington, Del.) using Film III Warm Red Ink (Environmental Inksand Coatings, Morganton, N.C.) on a Mark Andy 4200 flexographic press.The printed portion of the polyester roll is then coated with a solutionconsisting of 16 parts of aqueous 10% polyvinyl pyrrolidinone (PVP-90,ISP Technologies, Inc., Wayne, N.J.), 0.40 parts Sunsperse Violet (SunChemical, Cincinnati, Ohio), and 16 parts water using a #6 Meyer bar,and dried 1.5 minutes in an oven at 80° C. The film is then placed in acrystallizing dish containing ethyl acetate. A 10″×10″×12.5″ultrasonication bath (BLACKSTONE-NEY, PROT-0512H EP ultrasonic bathdriven by a 12T MultiSonik™ generator) is filled with about 4″ of waterand the dish containing the film is floated in the water andultrasonicated at 104 KHz for 5 minutes. The film is then removed fromthe dish and dried 1.5 minutes in an oven at 80° C. At the completion ofthe drying step, the film has lines of PVP coating that define anegative image of the originally printed positive image. The patternedpolyester is next sputter coated with ITO using a CHA Mark 50 rollcoater to deposit a 1250 angstroms thick ITO film. The ITO coatedpatterned polyester is then ultrasonicated for 3 minutes in a beakercontaining water placed in a Fisher #FS220H ultrasonicator (FisherScientific, Pittsburg, Pa.). The film is then rinsed with de-ionizedwater and dried by blowing the water off with a stream of air. Theresulting film has ITO structures in the shape of the originally printedpositive image.

In one embodiment, the process shown in FIGS. 6A-1 through 6F-2comprises sputter deposition of ITO film on a PET substrate having ahydrophilic coating, e.g., Melinex 582, and printed using warm red ink(Environmental Ink). In one embodiment, this combination of materialsallows the ITO to be stripped from undesired areas ultrasonically usinga water-based stripper.

In one embodiment, the water based stripper for ITO stripping could be asurfactant solution such as JEM-126 (sodium tripolyphosphate, sodiumsilicate, nonyl phenol ethoxylate, ethylene glycol monbutyl ether andsodium hydroxide), detergent formulation 409, hydroproxide, anddeveloper Shipley 453, etc.

In one embodiment, the ITO stripping rate depends on the solventconcentration, solvent temperature, and the position of the substratefilm relative to the ultrasound transducer.

In one embodiment, prior to the ITO sputter deposition, the ink printedPET surface is pre-treated with appropriate plasma. In one embodiment,such plasma pretreatment minimizes the generation of micro-cracks on thepatterned ITO structures during the ITO stripping process. In addition,such plasma pre-treatment may in one embodiment prevent ITO residue frombeing generated on the printed ink area as a result of removal of partof the printed ink pattern due to high-energy plasma, which may generateITO residue on the printed ink area during the stripping process.

In order to eliminate the optical impact of minor ink residue appearingon the stripped ITO surface, in one embodiment a colorless ink printedon the PET surface is preferred.

Any of the foregoing techniques for forming a patterned thin film designon a substrate may be used to form a patterned metallization layer on aplastic substrate to provide an IMD decorated film including such apatterned metallization layer in its design. The techniques areapplicable, without limitation, to both in-mold transfer and in-moldinsert IMD.

FIG. 7 is a flow chart illustrating a process used in one embodiment toform an in-mold transfer type IMD film, using one or more of thetechniques described herein for forming a patterned thin film structureon a substrate. The process begins in step 702, in which a PET substrateis coated with a release layer. In one embodiment, a release layer ofabout 0.1-3 μm, preferably 0.3-2 μm thickness is coated on a 2 mil PETsubstrate layer. In step 704, the treated substrate is coated with adurable layer for oil and scratch resistance. In one embodiment, thedurable layer is about 2 to 10 microns, preferably 4-8 μm thick. In step706, a patterned thin film portion of the IMD design is formed. In oneembodiment, step 706 comprises one or more of the techniques describedabove in connection with FIGS. 1 through 6D for forming a patterned thinfilm structure on a substrate. In one embodiment, step 706 comprisesforming a patterned metallization layer on the substrate, using one ofthe techniques described herein. In step 708, any additional pattern(s)is/are printed on the substrate using any suitable ink for visualeffects. The substrate and design are then coated with adhesive in step710. The resulting IMD decorated film may be used in an in-mold transferprocess to transfer the design to the injection-molded item.

FIG. 8 is a flow chart illustrating a process used in one embodiment toform an in-mold insert type IMD film, using one or more of thetechniques described herein for forming a patterned thin film structureon a substrate. In step 802, a patterned thin film portion of the IMDdesign is formed on, for example, a polycarbonate (PC) or acrylic (PMMA)substrate. In one embodiment, step 802 comprises one or more of thetechniques described above in connection with FIGS. 1 through 6D forforming a patterned thin film structure on a substrate. In oneembodiment, step 802 comprises forming a patterned metallization layeron the substrate, using one of the techniques described herein. In step804, any additional pattern(s) is/are printed on the substrate using anysuitable ink. The substrate and design are then coated in step 806 witha thin layer to protect the ink. The resulting IMD decorated film may beused in an in-mold insert process to transfer the design to theinjection-molded item.

The additional examples listed below (identified as Embodiments Athrough F to facilitate comparison) further illustrate the benefits, interms of the patterning of thin film and the related manufacturing andhandling processes, e.g., of including in the masking coating/ink are-dispersible particulate as described herein, such as in the processesdescribed above in connection with FIGS. 1 through 4B.

In an Embodiment A, the following masking layer composition was used foraluminum (Al) metal thin film patterning: 5.5 grams Celvol 203S (PVAfrom Celanese, Dallas, Tex., LMW, 87% hydrolysis), 5.5 grams PVP K-30(from ISP Corp., Wayne, N.J.), and 0.1 grams of Xanthan Gum (fromAllchem, Inc., Dalton, Ga.) were dissolved slowly at room temperatureinto 39.2 grams of de-ionized water. To the masking composition, 0.23grams of Silwet L-7608 (from OSi Specialties, Middlebury, Conn.), wasadded. The resultant solution was used as the masking coating/ink forprinting a pattern on a substrate for metallization, e.g., as describedherein.

In an Embodiment B, the following masking layer composition was used foraluminum (Al) metal thin film patterning: 3.0 grams of 20% dispersedsilica (Sylojet 703C, from Grace Davison, Columbia, Md.) was dilutedwith 36.2 grams of de-ionized water. To this solution, 5.2 grams Celvol203S, 5.2 grams PVP K-30 and 0.1 grams of Xanthan Gum were added slowlyat room temperature then mixed at high shear rate. Finally, 0.23 gramsof Silwet L-7608 was added. The resultant solution was used as themasking coating/ink for printing a pattern on a substrate formetallization, e.g., as described herein.

In Embodiments C-F, the same procedure and binders of Embodiment B wereused, except that the weight percent of Silica in the dried films werechanged to 10% in Embodiment C, 30% in Embodiment D, 60% in EmbodimentE, and 80% in Embodiment F.

For purposes of comparison, all of the masking solutions in theabove-described Embodiments A-F were screen printed on to a 2 milMelinex 453 PET film (ICI, UK) through a 330 mesh stencil to form anegative masking pattern. The roll-up properties of the printed filmwere evaluated by the blocking resistance at ambient and 50° C./80% RHconditions. The printed PET film was uniformly coated with an Al layerof 50 to 60 nm thickness by vapor deposition. Positive Al pattern wasdeveloped in water by selectively stripping off the Al layer on themasking layer to generate positive Al pattern on the area that was notprinted with the masking layer. The stripability or strippingselectivity is determined by the sharpness and shininess of theresultant Al image. The results are listed in Table 1 below (with theembodiment to which the data in each row applies indicated by the letterin the first column): TABLE 1 Binder Silica Screen Film Blocking FilmBlocking Stripability PVA/PVP (wt % in Printing at ambient after agingin of Al by K-30 (1:1) dried film) quality condition 50° C./80% RH WaterA 97  0% Good Blocking Blocking Good severely B 92  5% Good ExcellentGood Good C 87 10% Good Excellent Excellent Excellent D 67 30% GoodExcellent Excellent Excellent E 37 60% Good Excellent ExcellentExcellent F 17 80% Fair Excellent Excellent Fair-Good

It can be seen from Table 1 that the addition of the particulate silicafrom 5 wt % to 80 wt % based on the dried masking film improvessignificantly both blocking resistance of the masking layer and thestripability of the Al layer on the masking layer. The presence of theparticulate dispersion in the masking layer also resulted in highlyshiny Al lines with fine line width and excellent integrity.

In one embodiment, an in-mold decoration film, such as described abovein connection with FIG. 7, comprises a release layer prepared asfollows: 15.0 grams of CYMEL 303ULF (from Cytec Industries Inc., WestPaterson, N.J.) and 105 grams of MEK were mixed at 600 rpm for 5minutes. 0.3 grams of CYCAT600 (from Cytec Industries Inc., WestPaterson, N.J.) were added and stirred at 600 rpm for another 5 minutes.The resultant solution was then filtered with 0.2 micron filter andcoated onto a 1.42 mil PET (SH22, from SKC, South Korea) with a #4 Meyerbar for a targeted thickness of 1 μm. The coated film is then air driedfor 5 minutes and baked in oven at 130° C. for 10 minutes.

In one embodiment, an in-mold decoration film, such as described abovein connection with FIG. 7, comprises a durable layer prepared asfollows: 500 grams of 20% Elvacite 2041 (PMMA resin from LuciteInternational, Inc.) in MEK/cyclohexanone (weight ratio=9:1) were mixedthoroughly with 320 grams of 25% EB1290 (from UCB Chemicals) inMEK/cyclohexanone (weight ratio=9:1). To this solution, 67 grams ofMEK-ST (from Nissan Chemical) was added with mechanical agitation.Finally, 24 grams of 25% photo-initiator (Irgacure 907/Irgacure1800(=1:1, w/w, from Ciba Specialty Chemicals) in MEK/cyclohexanone (weightratio=9:1) and 89 grams of MEK/cyclohxanone (weight ratio=9:1) wereadded with agitation for additional 30 minutes. The solution was coatedon the release layer coated film with a #22 wired rod and the coatingwas dried in air for 30 min. and then at 65° C. for 10 min. to produce a6-7 μm (dry) thick durable layer coating.

In one embodiment, an in-mold decoration film, such as described abovein connection with FIG. 7, comprises a patterned aluminum layer formedas follows: The durable layer prepared as described in the paragraphimmediately above was printed with the masking layer of Embodiment Cdescribed above by screen printing, coated with an Al layer of about 60nm thick by vapor deposition, and a shiny, high resolution Al patternwas developed by rinsing with water to remove the Al on the printedmasking layer.

In one embodiment, the adhesive layer comprising an in-mold decorationfilm, such as described above in connection with FIG. 7, comprises anadhesive layer prepared as follows: 2.5 grams of Sancure 2710 (fromNoveon Inc., Cleveland, Ohio) and 7.5 grams of Dl water were mixedthoroughly and coated onto a patterned Al layer prepared as described inthe paragraph immediately above using a #16 Meyer bar with a targetedthickness of 2 to 3 μm. The coated film was then dried in oven at 90degree C. for 1 minute.

In one embodiment, a multilayer film formed as described in the fourparagraphs immediately above was fed into an injection mold, and PMMAresin was injection molded onto the adhesive layer. The durable layerand patterned Al layer were transferred completely onto the moldedpieces after the release film was peeled off.

Although the foregoing invention has been described in some detail forpurposes of clarity of understanding, it will be apparent that certainchanges and modifications may be practiced within the scope of theappended claims. It should be noted that there are many alternative waysof implementing both the process and apparatus of the present invention.Accordingly, the present embodiments are to be considered asillustrative and not restrictive, and the invention is not to be limitedto the details given herein, but may be modified within the scope andequivalents of the appended claims.

1. A process for forming a patterned thin film structure on a substrate,comprising: printing a pattern on the substrate using a strippablematerial comprising-5-80% by weight of a re-dispersible particulate, theprinted strippable material defining a negative image of a decorativedesign to be formed on the substrate, such that the printed strippablematerial is present in areas on the substrate where the thin filmstructure is not to be formed and the printed strippable material issubstantially not present in the area on the substrate where the thinfilm structure is to be formed; depositing a thin film material on thepatterned substrate; and stripping the strippable material from thesubstrate; whereby the strippable material and any thin film materialformed thereon are removed by said stripping leaving behind the thinfilm structure formed on the substrate in the shape of said decorativedesign; wherein the substrate and the patterned thin film structureformed thereon are suitable for use as an IMD decorated film.
 2. Theprocess for forming a patterned thin film structure on a substrate asrecited in claim 1, wherein the strippable material comprises 10-60% byweight of said re-dispersible particulate.
 3. The process for forming apatterned thin film structure on a substrate as recited in claim 1,wherein the strippable material comprises a water soluble or waterdispersible polymer as a binder.
 4. The process for forming a patternedthin film structure on a substrate as recited in claim 3, wherein saidwater soluble or water dispersible polymer is selected from the groupconsisting of polyvinyl alcohol, polyvinylpyrrolidone, polyvinylpyridine, polyacrylic acid, polymethacrylic acid, polyacrylamide,polyethylene glycol, poly(ethylene-co-maleic anhydride), poly (vinylether-co-maleic anhydride), poly(styrene-co-maleic anhydride),poly(butyelene-co-itaconic acid), PEOX, polystyrene sulfonate, cellulosederivatives, xanthan gum, gum Arabic, gelatin, lecitin, and copolymersthereof.
 5. The process for forming a patterned thin film structure on asubstrate as recited in claim 3, wherein said water soluble or waterdispersible polymer comprises a water dispersible polymer selected fromthe group consisting of water- or alkaline-dispersible waxes,polyolefin, and acrylic latexes or dispersions.
 6. The process forforming a patterned thin film structure on a substrate as recited inclaim 1, wherein the strippable material comprises a solvent soluble orsolvent dispersible polymer as a binder.
 7. The process for forming apatterned thin film structure on a substrate as recited in claim 1,wherein the re-dispersible particulate is derived from silica, CaCO₃,CaSO₄, BaSO₄, Al₂O₃, TiO₂, hollow-spheres, non-film-forming latexes ordispersions, inorganic pigment, or organic pigment.
 8. The process forforming a patterned thin film structure on a substrate as recited inclaim 1, wherein the re-dispersible particulate is a polymeric particleor a polymeric composite particle.
 9. The process for forming apatterned thin film structure on a substrate as recited in claim 1,wherein the strippable material further comprises an additive selectedfrom the group consisting of surfactants, dyes, curing agents, andplasticizers; whereby the presence of said additive facilitates thestripping of the strippable material subsequent to the deposition of thethin film material.
 10. The process for forming a patterned thin filmstructure on a substrate as recited in claim 1, wherein the thin filmmaterial is non-conductive.
 11. The process for forming a patterned thinfilm structure on a substrate as recited in claim 1, wherein the thinfilm material is semi-conductive.
 12. The process for forming apatterned thin film structure on a substrate as recited in claim 1,wherein the thin film material is conductive.
 13. The process forforming a patterned thin film structure on a substrate as recited inclaim 12, wherein the conductive thin film material is a materialselected from the group consisting of metals, metal oxides, and alloysor multilayer composites thereof.
 14. The process for forming apatterned thin film structure on a substrate as recited in claim 12,wherein the conductive thin film material is a metal selected from thegroup consisting of aluminum, copper, zinc, tin, molybdenum, nickel,chromium, silver, gold, iron, indium, thallium, titanium, tantalum,tungsten, rhodium, palladium, platinum and cobalt.
 15. The process forforming a patterned thin film structure on a substrate as recited inclaim 12, wherein the conductive thin film material is a metal oxide orsulfide selected from the group consisting of indium tin oxide (ITO),indium zinc oxide (IZO), aluminum zinc oxide, gadolinium indium oxide,tin oxide, fluorine-doped indium oxide and zinc sulfide.
 16. The processfor forming a patterned thin film structure on a substrate as recited inclaim 1, wherein the step of depositing the thin film material comprisessputtering, vapor deposition, vacuum deposition, electroplating,electro-less plating or electroforming.
 17. The process for forming apatterned thin film structure on a substrate as recited in claim 1,wherein the step of printing comprises flexographic printing,driographic printing, electro photographic printing, lithographicprinting, gravure printing, thermal printing, inkjet printing, screenprinting or stamp printing.
 18. The process for forming a patterned thinfilm structure on a substrate as recited in claim 1, wherein thesubstrate comprises a plastic substrate.
 19. The process for forming apatterned thin film structure on a substrate as recited in claim 18,wherein the plastic substrate comprises a portion of a roll of plasticsubstrate.
 20. The process for forming a patterned thin film structureon a substrate as recited in claim 19, wherein the process for forming apatterned thin film structure on the substrate is a component part of aroll-to-roll process for fabricating the IMD decorated film.
 21. Theprocess for forming a patterned thin film structure on a substrate asrecited in claim 1, wherein the substrate comprises a polyethyleneterephthalate (PET) film.
 22. The process for forming a patterned thinfilm structure on a substrate as recited in claim 21, further comprisingperforming the following steps prior to forming the patterned thin filmstructure on the substrate: treating or coating the PET film with arelease agent or coating; and coating the treated or coated PET filmwith a durable layer to provide oil and scratch resistance.
 23. Theprocess for forming a patterned thin film structure on a substrate asrecited in claim 21, further comprising printing on the substrate asecond decorative design using a printable material other than the thinfilm material.
 24. The process for forming a patterned thin filmstructure on a substrate as recited in claim 21, further comprisingcoating the IMD decorated film with an adhesive to form an in-moldtransfer film.
 25. The process for forming a patterned thin filmstructure on a substrate as recited in claim 1, wherein the substratecomprises a polycarbonate (PC) substrate.
 26. The process for forming apatterned thin film structure on a substrate as recited in claim 25,further comprising coating the IMD decorated film with a thin protectivelayer.
 27. The process for forming a patterned thin film structure on asubstrate as recited in claim 1, wherein the step of stripping comprisesusing a solvent to remove the strippable material.
 28. The process forforming a patterned thin film structure on a substrate as recited inclaim 27, wherein the solvent is selected from the group consisting ofwater, aqueous solutions, alcohols, ketones, esters, ethers, amides,hydrocarbons, alkyl benzenes, pyrrolidones, sulfones, DMSO, and mixturesor derivatives thereof.
 29. The process for forming a patterned thinfilm structure on a substrate as recited in claim 1, wherein the step ofstripping comprises using mechanical pressure to remove the strippablematerial.
 30. The process for forming a patterned thin film structure ona substrate as recited in claim 29, wherein using mechanical pressurecomprises brushing or using a spray nozzle.
 31. The process for forminga patterned thin film structure on a substrate as recited in claim 1,wherein the step of stripping comprises: applying an adhesive layerhaving a higher adhesive strength with respect to the thin film materialand/or strippable material than the adhesive strength of the strippablematerial to the substrate; and removing the strippable material and anythin film material deposited thereon by peeling off the adhesive layer.32. The process for forming a patterned thin film structure on asubstrate as recited in claim 1, wherein the step of strippingcomprises: applying an adhesive layer to the substrate after thedepositing step; and removing the thin film material with the strippablematerial by peeling off the adhesive layer.
 33. The process for forminga patterned thin film structure on a substrate as recited in claim 32,wherein the cohesion strength of the thin film material and the adhesionstrength between thin film material and the substrate are stronger thanany of the three forces: the cohesion strength of the strippablematerial, the adhesion strength between the thin film material and thestrippable material, and the adhesion strength between the strippablematerial and the substrate.
 34. A process for forming patterned thinfilm structures on a substrate, comprising: printing a first pattern ona first surface of the substrate using a strippable material comprising10-60% by weight of a re-dispersible particulate, the first pattern ofthe strippable material defining a negative image of a first thin filmstructure to be formed on the first surface of the substrate; depositinga thin film material on the patterned first surface of the substrate;stripping the first pattern of the strippable material from thesubstrate; printing a second pattern on a second surface of thesubstrate using a strippable material comprising 10-60% by weight of are-dispersible particulate, the second pattern of the strippablematerial defining a negative image of a second thin film structure to beformed on the second surface of the substrate; depositing a thin filmmaterial on the patterned second surface of the substrate; and strippingthe second pattern of the strippable material from the substrate;whereby the first pattern of the strippable material, the second patternof the strippable material, and any thin film material formed on eitherthe first or the second pattern of the strippable material are removedleaving behind the first thin film structure on the first surface of thesubstrate and the second thin film structure on the second surface ofthe substrate; wherein the first thin film structure comprises a firstdecorative design, the second thin film structure comprises a seconddecorative design, and the substrate and the patterned thin filmstructures formed thereon are suitable for use as an IMD decorated film.35. A process for forming patterned thin film structures on a substrate,comprising: printing a first pattern on a first surface of the substrateusing a strippable material comprising 10-60% by weight of are-dispersible particulate, the first pattern of the strippable materialdefining a negative image of a first thin film structure to be formed onthe first surface of the substrate; printing a second pattern on asecond surface of the substrate using a strippable material comprising10-60% by weight of a re-dispersible particulate, the second pattern ofthe strippable material defining a negative image of a second thin filmstructure to be formed on the second surface of the substrate;depositing a thin film material on the patterned first surface and onthe patterned second surface of the substrate; and stripping the firstpattern and second pattern of the strippable material from thesubstrate; whereby the first pattern of the strippable material, thesecond pattern of the strippable material, and any thin film materialformed on either the first or the second pattern of the strippablematerial are removed leaving behind the first thin film structure on thefirst surface of the substrate and the second thin film structure on thesecond surface of the substrate; and wherein the first thin filmstructure comprises a first decorative design, the second thin filmstructure comprises a second decorative design, and the substrate andthe patterned thin film structures formed thereon are suitable for useas an IMD decorated film.
 36. A process for forming a patterned thinfilm structure on a substrate, comprising: printing a pattern on thesubstrate using a printable material, the printed printable materialdefining a positive image of a decorative design to be formed on thesubstrate, such that the printable material is printed in areas wherethe thin film structure is to be formed; depositing a thin film materialon the patterned substrate, wherein the thin film material, theprintable material, and the substrate are chosen so that the thin filmmaterial adheres more strongly to the printable material than to thesubstrate; and stripping the thin film material formed directly on thesubstrate using a stripping process that does not strip the thin filmmaterial from the printable material such that the thin film materialremains on the printable material used to define the pattern in whichthe thin film structure is to be formed; wherein the substrate and thepatterned thin film structure formed thereon are suitable for use as anIMD decorated film.
 37. The process for forming a patterned thin filmstructure on a substrate as recited in claim 36, wherein the printablematerial comprises a primer coating, adhesive, tie coat, or adhesionpromoting material.
 38. The process for forming a patterned thin filmstructure on a substrate as recited in claim 36, wherein the printablematerial comprises ink.
 39. The process for forming a patterned thinfilm structure on a substrate as recited in claim 36, wherein theprintable material is radiation curable or thermal curable.
 40. Theprocess for forming a patterned thin film structure on a substrate asrecited in claim 36, wherein the stripping process comprises using asolvent.
 41. The process for forming a patterned thin film structure ona substrate as recited in claim 36, wherein the stripping processcomprises using mechanical pressure.
 42. The process for forming apatterned thin film structure on a substrate as recited in claim 41,wherein using mechanical pressure comprises brushing or using a spraynozzle.
 43. The process for forming a patterned thin film structure on asubstrate as recited in claim 36, wherein the printable materialcomprises a first adhesive, adhesion promoting or tie material and thestripping process comprises: applying a second adhesive layer to thesubstrate after the thin film deposition step; and removing the thinfilm material without removing the first adhesive, adhesion promoting ortie material by peeling off the second adhesive layer.
 44. The processfor forming a patterned thin film structure on a substrate as recited inclaim 43, wherein the adhesion strength between thin film material andthe substrate is the weakest as compared to the cohesion strength of thesecond adhesive layer, the cohesion strength of the first adhesive,adhesion promoting or tie material, the cohesion strength of the thinfilm material, the adhesion strength between the thin film material andthe second adhesive layer, and the adhesion between the thin filmmaterial and the first adhesive, adhesion promoting or tie material.